Jacob s



JACOB S. ROBESON, F PENNING'TON, JERSEY.

MANUFACTURE OF DYESTUFFS.

ll'o Drawing.

. To all whom it may concern:

Be it known that I, JAcoB S. RoBEsoN, a citizen of the United States, residing at Pennington, in the county of Mercer and State of New Jersey, have invented certain new and useful Improvements in the Manufaeture of 'Dyestufls, of which the following is a specification.

This invention relates to the manufacture ofdyestuifs; and it comprises a method of producing dyestufl's of the class known as sulfur dyes wherein a heavy metal or an earth metal derivative of the characteristic organic matters of sulfite waste liquor is heated with an alkaline sulfid in the presence of sufiicient sulfur and it also comprises as a new dyestuif, a sulfur dye containing a heavy metal (that is a compound of one of the common heavy metals) and derivativesof the characteristic organic matters of sulfite waste liquor, such dyestufi bein a gray black powder, soluble in water, 9.11% directly dyeing cotton and other vegetable fibers brown or black; all as more fully hereinafter set forth and as claimed.

In the manufacture'of paper one of the common methods is digestion of the wood with a solution of an acid sulfite; generally acid sulfite or calcium (bisulfite of lime) though a solution containing acid sulfites of calcium and of magnesium is sometimes used where dolomitic lime is used for making the sulfite liquor. About half the organic matter of the wood goes into solution, uniting with the'sulfur and bases present to form complex new bodies. For the sake of a name, the portion of the wood which goes into solution is usually, called lignone; and the complex new bodies are termed lignosulfonates in the art; lignosulfonate of calcium for example. It is material containing these characteristic organic components of sulfite waste liquor that I use in the pres ent invention.

In the art, sulfite waste liquor is ordinarily neutralized with lime and evaporated to make commercial products; these commercial products ranging from a thick vis cous liquid of Baum to a semi-solid or dry solid material. It is a concentrated product of this nature which I advantageously use in the present invention although the original or unconcentrated sulfite waste liquor may also be used.-

On mixing sulfite liquor or its dried or concentrated preparations with sulf ur a d Specification of Letters Patent.

Patented Sept, as, rare;

Application filed April 25, 1916. Serial No. 93,474.

sodium sulfid and fusing the mixture, dyestufis can be made which will color cotton black. better materials having better dyeing propert1es and yielding a better color may be made by substituting for the lime in the sulfite liquor another and non-alkaline base; this base being best one of the heavy metal bases, although an earth metal basefsuch as alumina, may be used.

As stated, the characteristic organic mat- I have found however that much ters of the sulfite Waste liquor preparations are usually called lignosulfonates and they have in a general way the properties of salts of sulfonic acids; these acids forming soluble salts with most or all of the heavy metal bases. The lignosulfonates of these other bases form better sulfur dyes than do the lignosulfonates of lime. The actions in making and recovering the dye go forward more smoothly and the product is better. I therefore in the present invention treat the sulfite waste liquor in solution with a salt of a heavy metal with an acid capable of forming insoluble lime salts. A solution of a lignosulfonate on admixture with a solution of such a salt gives by double decomposition a soluble lignosulfonate which re mains in solution and an insoluble precipitate of,a lime salt which can be separated by decantation, filtering, For the present purposes, the sulfates are well adapted.

l have used alumnium sulfate, iron sulfate, zinc sulfate, copper sulfate, and many others. Each gives a specific dyestufi"; and the shade and other properties of each particular preparation depend in a measure upon the particular salt used. it is not necessary to use the sulfates since many other salts, such as the oxalates, may be used. Or the oxids, hydrates or carbonates of the particular metals desired may be employed.

' But the sulfates are by far the most convenient salts since they are mostly soluble and give a precipitate of calcium sulfate which is easily separated.

In a specific embodiment of the present invention producing a sulfur dye containing iron, "I take 100 pounds of commercial 30 Baum concentrated sulfite waste liquor. Or I may take the corresponding amount of one of the commercial dried preparations and dissolve it in water. The liquid in either case is mixed with 10 pounds of ordinary ferronssulfatedgreeimitrioly dissolved in so pounds of water. By a metathetical exchange, sulfate of calcium is formed and precipitates while lignosulfonate of iron in corresponding amount remains in solution. The precipitate is now separated from the liquid, which may be done by settling and decanting; by filter-pressing, etc. 1 thereafter concentrate the clear liquid to some extent and mingle it with salt (NaGl) or sodium sulfate. At concentrated solution of either salt may be used. For 100 parts by weight of the clear liquid made from 30 Baum concentrated sulfite waste liquor about parts by weight of sodium chlorid is usually required. While, as stated, the lignosulfonates are soluble in water, yet they are not soluble in concentrated saline solufionsgand the addition of the salt to the solution therefore throws the lignosulfonate out of solution, giving a fiocky or curdy precipitate which is readily filterpressed and handled. The precipitate s separated from the mother llQllOfand is filtenpressed and dried. The cake is powdered and mingled with commercial sodium sulfid and sulfur, using for the Eprecipitate from 100 pounds by weight of t e original clear liquid, about 42 pounds of commercial sodium sulfid and 42 pounds of sulfur. This mixture is fused or melted at a low heat, cooled and pulverized. The mixture thus formed contains a dyestuff derived from the characteristic organic matters of sulfite waste liquor and iron, both being in union with sulfur. It is a black material soluble in water. Tn making a solution however it is best to use a little sodium suliid dissolved in the water. The solution directly dyes cotton a brownish black, fast to sun and alkali. Tt does not directly dye wool and silk and for use with animal fibers they should be mordanted in appropriate ways.

dyeing with this new dyestuif the cotton is simply immersed in warm or hot water solutions of the material and on being taken out and washed is of the expected color, without further treatment.

Another preparation may be made by tak ing the same amount of sulfite waste liquor and adding about 8 pounds of commerclal crvstallized aluminum sulfate. The rest of ooeratiou is as described ante. The dye produced colors cotton a reddish brown By using copper sulfate in of 9 pounds for every 50 pounds of dry matter containedin the sulfite waste liquor preparation a dye is obtained which colors cotton a seal brown.

By treating sulfite waste liquor solution with zinc sulfate iii. the proportion of 10.5 ounds crystallized. ccnnnercial zinc sulfate I 100 gallons f commercial 30 "to waste liquor a dye may be procolors cotton a gray brown.

. converted into line sulfid to make a sulfur the proportion asserts By substituting oxalates of the metals named for the corresponding sulfates, a somewhat cleaner separation of the lime may be accomplished. be used in treating sulfite liquor to remove the lime and make the desired lignosulfonates. For example, if ordinary commercial sulfite liquor of 30 Baum be heated for a time with commercial carbonate of copper at a temperature of, say, 100 6., the calcium and magnesium of the sulfite liquor are the corresponding carbonates The carbonates may also while copper goes into solution as lignosulfonate. fonate may be treated in the manner scribed ante.

What ll claim is 1. The process of making dyestuffs which comprises removing the calcium of sulfite waste liquor while substituting another and non-alkaline base therefor, and heating the resultant product with sulfpr and an alka- 2. The process of making dyestuffs which comprises treating a solution of sulfite waste preparation with a salt of a non-alkaline base with an acid forming insoluble lime salts, removing the precipitate formed and heating the resultant product with sulfur and an alkaline sulfid to make a sulfur dye.

3. The process of making dyestuffs which The solution of copper lignosu1 comprises treating a solution of sulfite waste preparation with a salt of a non-alkaline base with an acid forming insoluble lime salts, removing the precipitate formed a d heating the resultant product with sulfirr and sodium sulfid to make a sulfur dye.

v 4. The process of making dyestufis which comprises mingling a solution of the characteristic organic matters of sulfite waste liquors with a soluble sulfate of a non-alkaline base, removing the calcium sulfate precipitated, and heating the com ounds formed with sulfur and sodium- 5111 id to make a sulfur dye.

5. The process of making dyestuffs which comprises mingling a solution of the characteristic organic matters of sulfite waste liquors with a solution of a heavy metal, removing the calcium sulfate precipitated, and heating the compounds formed with sulfur and sodium sulfid to make a sulfur dye.

6. The process of making dyestuffs which comprises precipitating the lime of sulfite waste liquor with a solution of a soluble heavy metal sulfate, removing the calcium sulfate formed, precipitating out the soluble matters with a suitable salt, and heating the sulfate of a precipitated matter with sulfur and sodium fite waste liquor with ferrous suiiraie wamm ing the recipitafced sufifmzei and the resz ue wmah sulfur and am afiixaizm sulfid.

10. The prccess of making a saluhle suifuy dye which comprises mixmg sulfim wasbs liquor with ferrous sulfate sapamtin 0% the precipitam fermefi, mixin with Q, a memain'mg liquor a, concenimte saiim suin tion, separating 0115: the precipimia formed and, aftsr dry: am Bowdsrlng, iwwing it with sulfur an an afiaiim suiiid.

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